Ester of sulphosuccinic acid



vApril 13, `1943. 1 H, FLTT Y- 2,316,2rf1` ESTER oF sULPHOsUCcNIc ACID y Filed Nov. zo,` 1940 p. Estera or sulphoaliphatic dicarboxylic acids I are known in which the carboxyl groups are es-i q terifled by long-chain alcohols. :Thus the monocetyl, the dilauryl and the distearyl esters of sulphosuccinic acid in the are known.

` Patented Apr. 13, .1943

. Lawrence Flatt, Hamburg, N. AY., assignorto- AllledChemical s Dye Corporation, a corporaf s 'tion of New York Application November so, 1940, serial No. 367,965

warm. (c1. 26o- 481) f This invention relates tol a small` new 'groupof compoundslying within the `large class of esters of `sulpho-allphatic dicarboxylic `acids that are useful as wetting agents`,"emulslfying` agents and detergents. The new group of compounds finds particular use as washing agents, `especially for ...regenerated cellulose rayon, and as dispersing agents for water-insoluble organic coloring agents, especially for dyes ior cellulose esters, such `as cellulose acetate.

form of their sodium salts The'present invention is based on the discovery thatl the monocetyl esters of sulphosuccinic acids phurous acid with monocetyl carboxylic esters of constitute a group ofcompoundspossessing outi standingly desirable properties much" `beyond whatwould be expected, judging by the proper`` tieszbf the closely homologous compounds. The monocetyl esters of sulphosuccinic acidsgin the form of the freefacidsf correspond withithe for- V Y mula: A, cnaocooncncoon `irrwhichli and Y` are `each selected ironrth'e group consisting of hydrogen, methyl andV `-SOaH but at least `one lof X' and Y is fSOaH. i `(As employed` herein, the term cety denotes i the normal primary hexadecyl radical Y Y crmCmmCrn-J i `I have i'ound that the presencein said esters of the particular combination of a single alkyl chain ,l of 16 carbon atoms and a free carboxyl group.

, `(in the acid or saltform) as welllas a ireesulphoi, i

group (in the acid or salt forxnlimparts desircarboxylic ester of monosulpho-succinic acid.

The new compounds may be .prepared-ibyV methods similar to the known methodsliorvmaking known members of theclass or esters of sul# pho-aliphatic `dicarboulic acids. Preferably` `the i compounds ot this invention are preparedbythe reaction` of lsulphurous acid or'V a water-soluble( Q sulphite (such asian ammonium salt,` a sodium or 20 A is hydrogen ora methyl group; and the other Agis halogen, ora sulphate or phosphate group.

l For detergent purposes'inwatenthey are 'very other alkali metal salt, or "an organic baseV salt Y of sulphurous acid) with a monocetyl ester of maleicor fumaric acid. The reactionyields the monocetyl carboxylic ester of monsulpho-suc-f cinic acid in the form of the free acid or a rsalt in which the salt-forming cation'is themetal,

ammonium or organic cation of the reacting sul-f phite.` i

The compounds of this invention also may be prepared by reacting bisulphites, sulphites or sulsuccinic acid containing in the succinic acid residue a replaceable atom orgroup; for example, the esters winch are represented by the follow- 15 ing formula:

` catraococnoaoooiue l l f in which Me represents-hydrogen or its chemical equivalente! a salt-formingmetal ori group; one

'Ihe compounds of the ,invention can be Aapplied individuallyor as mixtures at suitable concentrations for a very large number and variety ot purposes. They are characterized by specially highdetergent power,` and they show unusual cleansing action in many cases; for example, in l Vwashinl; regeneratedcellulose, where soapless detergentsfas a class are'` deiicient.` `Because of Y these., characteristics, they `are admirably suited,

for' incorporation lin detergent preparations in which enhanced washing qualities are-desired.

effective even at low concentration and are usu'- ally applied `in concentrations whichrange from 0.05 to 0.2 percent. They can be used at such concentrations for laundryV Work; personal use;

dlsperslngdyes in dyeing and printing prepara- V tions and applications; germcidal compositions;

` insecticidal spraysydispersing materialsin the lester Silks. Y Y y They may be used as advantageous dlspersing assistants in lubricants, treating and spinning xrianufacture` of iinely divirlerl` pigments: dispersingactive' substances for impregnated tex- Y i tile materials, wood,`leather; etc.;` aiding in the y 45- `dyeing or coloration Afot cellulose acetateV and other esters or materialscontaining acetate and oilsldustlaying, sprays 4and compositions, and

i'n'the suspension' of pigments .ink lacquers.

`Becausefof their unusual cleaning'properties, the compounds :of'this invention are specially Y p suitable ingredients for cosmetic preparations.

"These compounds, by

virtue of their rapid:

acetate.

less solvents.'

emulsifying and dispersing properties, are very useful and valuable ingredients of dry preparations of dyestuis and coloring matters which are applied as dispersions in water for dyeing or coloring natural silk or materials which are made of orcontain cellulose esters, especially cellulose In ksuch `dye compositions the com pounds of thisinvention play a two-fold part: (1) they disrupt the dyestui particles Vwhenthe dry mixtures r'are added to water, and thereby prevent conglomeration of dye particles; and (2) they disperse thoroughly the dye particles throughout the dye bath liquid and thereby as sure, without the aid of vigorous mechanical agitation, uniform distribution of dyestui throughout the dye bath, and uniform dyeing of material dyed therein.

The salts of the monocetyl'carboxylic ester of;

monosulphofsuccnic acid which contain ammonium, alkali metal or Water-soluble organic.` base cations'are generally` soluble in water. They are also soluble in organic solvents. such as alcohol, benzene', toluene, etc. In the pure form the salts yield practically colorless solutions in color-` They can be recrystallizedlfrom. their aqueous solutions.

The salts of 'the monocetyl. carboxylic :esterA of monosulpho-succinic acid are unexpectedly outstanding in their detergent and foaming properties. They are especially preferred in compositions and their applications for the preparation, cleansing, nishing or .other rtreatment of regenerated'cellulose and materials 'containing re generated cellulose. Y f' The invention is illustrated by the following examples in which parts are by weight:

EXAMPLE 1 ing the following composition was added to each lreaction mixture, which' contained the monoalkyl ester vof maleic acid corresponding with the alcohol employed: Y Y

A mixture of 484 parts (2 mols) of commercial l cetyl alcohol which was derived from sperm oil and 200 parts (2.02 mols) of maleic anhydride is agitated and. heated by means of a boiling water bath for 3 hours. The product so obtained. is an acidester of commercial cetyl alcohol and for convenience is referred to as monocetyl m-aleate.

S80-parts (2 mols) ofkmonocetyl maleate are heated to refluxingwithv 252 parts (2 niels) of sodium sulphite in 2400parts of water yfor 4 hours. The mixture becomes'a clear, solution in l hour. 'Ihere is some foaming during the boiling.` The temperature of the mixture is reduced as necessary to control foaming. Good agita- "tion is maintained throughout the heating period. 'In four hours, there is no free sodium sulphite cinto [intonaco o can sogut The commercial cetyl alcohol described and used in preparing the product above contains approximately 22 per cent of unsaturatedl alcohols (probably oleyl alcohol) and smaller. amounts of `Stearyl and myristyl alcohols. Consequently the 1 of the product. Each solution was testedin-tbe detergent product presumably contains a sub stantial proportion of disodium mono-oleyl monosulphosuccinate and minor amounts of disodium monostearyl monosulphosuccinate' and disodium monomyristyl monosulphosucoinate. v Y

The resulting mixture is a particularlyeiective washing agent, its unusually high detergent qualities being due to the presence therein of an effective amount of disodium monocetyl monosulphosuccinate. i y

The following example-shows the marked end `entirely unexpected and unforeseeable superiority in ldetergency and foaming properties of the monocetyl ester of monosulpho-succinic acid when compared with the homologous and closely related esters containing, respectively, l2, 14 and 13 carbon yatoms in a similar alkyl chain.

' EXAMPLE 2 The following normal primary alcohols in their respective following amounts (one mol) were eachmixed with 103 parts of maleic anhydride (1.05 Idols) and each mixture was agitated and heated at to 105 C. for 2 hours:

Alcohol: Y Parts by weight Lauryl (B. P. -147 C. at l5 mm.) 186 Myrstyl (B. P. 16'7-170 C. at l5 mm.) 214 Cetyl (B. P. 18L189 C. at 15 mm.) 242 Stearyl (Eastman pure) v 270 After the heating period was over, a solution hav- Sodium bisulphitel09 parts (1.05 mois). Sodium hydroxide-approximately 82 parts of a 50% .aqueous solution: sufficient to make the solution slightly pink to phenolphthalein (approximately 1.05 mols) Water-approximately 440 parts. Y

The 'reaction Inixture'was agitated atl 100 to 105 C. for 3 hours (unless foaming was excessive, Vin which ease the temperature vwas lowered to 9'? to 100.2C.), the solution was diluted to about 20 per cent strength, adjusted'to neutrality to delta paper, and drum dried. To purify the products, they wereV each dissolved in water to forma y10 per cent solution, andagitated at55 to 60 C. for ahalf hour with 10 per cent of decolorizing charcoal (Darcol) based on the weight of the produ'ct. The solution was iiltered through Supercel and. drum dried.

To compare the foaming action of the resulting products, aqueous solutions of each of the products were yprepared containing 0.05%' by weight following manner: 1

50 cc. of the solution to be tested were placed in a testing apparatus consisting of a 500 cc. cylindrical graduate and a plunger consistingV of a No. 9irubberstopper` or cork (having Ia top.Y Ydiameter of aboutone inch. and three-quarters,

a bottom diameter of about an inch and seven- 'sixteentha anda height of about one inch)V t mounted on its center on a glass `rod extending well above the top of the graduate. The stopper or cork-Was of such a size that it slipped easily inside the cylinder. Foam was generated by plungingthe stopper into, and withdrawing it from, the solution in uniform strokes between the bottom andthe 200 cc. mark of the graduate at a rateof about two strokes per second'for 3() seconds. Y The total volume of foam and liquid and the volume of liquid which had separated at the bottom of the graduate were measured after standing for three minutes. The solutions were tested at substantially the same temperature.

The results are V'set out in the following Table'I.

Table I Percent V l vo uma o uma o Estar retained ioam in cc.

asioam f Disodlum monolauryl monosulphosuccii nate (Cn) 16 65 Disodium monomyristyl lnonosulphosuc` cinato u) 2l 105 Disodium monocetyl monosulphosuccinate (Cn) 39 100 `Disodium monostearyl monosulphosuccinate (Cu) 14 75 To compare the detergency of` theI products,

`wool washing tests were conducted as follows:

v Bots.

woolen worsted was uniformly soiled in a soi vng bath consisting of a mixture of 4 liters o1' carbon tetrachloride, 1/4 gram of lamp black,

35 cc. of mineral oil (white oil) and 'I1/` grams of .tallow. After drying in an'oven at 20 C. for 1 hour and aging for a week in the atmosphere at i room temperature, the clothv was cut into pieces of approximatelyequal size-(4 inches by 4 inches)` and readings were taken of the intensity of reected light (brightness) with a Lange Universal then washed in a Launder-ometer" in the fol-,-

lowing manner; A piece ofthe soiled"`cloth,yv as `placed in a pint preserving jar containing 200cc.

of an aqueous solution of the product to beltested and 125 quarter-inch Monel metal b'llsrandthe reflectometer. VPiecesoi.' `the soiled V.cloth were appear as Figs.' 1 and 2 of the drawing, respectively, which are self-explanatory.

The following example illustrates the superiority of disodium monocetyl monosulphosuccinate for washing regenerated cellulose.

EXAMPLE: 3

A mixture which was chiefly disodium monooetylA monosulphosucoinate` was prepared from commencial cetyl alcohol by following substantially the procedure of Example 2, except that when preparing the-monocetyl acid ester 1.05 mois of cetyl alcoholper mol of maleic anhydride were Rayon fiat crepe (du Pont Dulite) was cut into strips each 21 feet long and 9 inches wide; the `stripswere sewn into an endless belt whichwas soiled with the aid of an experimental soiling machine, @by being passed ten times through a. solution composed 01.4000 .'cc. of carbon tetrachloride, 6 gramsv of tallow, 20 grams of NuJol" .(reiined white-foil) and 4 grams of lamp black, and through a wringer after each passage through the soiling mixture. 'I'he uniformly soiled strip was driedin a steam ovenior one hour and aged five daysL at room temperature; The resulting soiled cloth was tested for.` fbrightness using a Zeiss-Pulfrich .photoxnetn` ',The. same instrument was used to detenmine the` brightness of samples of the soiled cloth afterfftheyghad been l l The detergent qualities of the mixture containyas Jar `was covered and rotated for a .period of 30` y minutes at 50 C. Tests were made with solutions preparedby adding 0.2 gram of the product being tested plus 0.2 gram o f sodium sulphateil) to 200 cc. of distilled water, and (2)v to 200 cc. of distilled water to which 1 cc. of 5 per centaqueous calcium chloride solution had been 4added- (equivaient to water of 12 hardness). The washed pieces of cloth were rinsed with cold water, and

. dried in the air. Readings were again taken with the refiectometer.. The` difference in readings.

representing increased brightness, is a measure of th@ detergency of the products.

The results are set out in the following Table 1I.

Table `II Dete `ency (increase in rightness) Ester 12 hard Soft water wam,

^ Disodium monolauryl monosulphosucclnate 6.6 t, t 2 `Dcisigdiurn monomyristyl monosulphosuc- 7 5 Disodium m'ot-Tbi nate s y. l 11.5 14.5 Disodium monostearyl monosulpbosuoci-- l t nate (Cn) A.'.- 8 2.5

In order to illustrate more clearly the superior foaming and detergent properties of the mono-` cetyl ester of monosulpho-succinic acid, the re suits of the above tests set out in TablesI and II were .plotted as graphs. 'I'he resulting graphs .ing chiefly `disodium monocetyl nfimosulphosuccinate,'prepared as described above`,were compared with those of Luxa sodium soap manufactured by Lever Brothers and extensively advertised as a highly effective washing agent-and with disodium monolauryl monosulphosuccinate prepared from commercial lauryl alcohol substantially -by the method of Example 2. Aqueous solutions were prepared, each containing 0.18 part of the product to be tested dissolved inlOO .parts of water having 2.5 degrees of hardness (American. scale). wash a Piece of soiled cloth nine inches square. The washing was conducted by dipping the cloth, moving it around and squeezing the cloth in the solution, then withdrawing the cloth and wringding it out by hand aboutonce every minute. This procedure was continued for 5 minutes. The cloth was then rinsed in distilled water for one half minute and Wrung out -by hand. Finally,the cloth was hung indoors until dry. Detergentl action of the solutions was measured by thejincreases in brightness of the cloths eiected bythe washings. The results are shown in Table III.

cable `111 Detergency Product 1mi ness) 'mur' 6.o Disodium monocetyl monosu'lshosuocinste 13. 4 Disodium monolauryl monos phosuccinate 6.5

Iclaim: Disodium monocetyl-monosulphosuccinate. i

LAWRENCE H. Fm'rr.

One lpint of solution wasused to` 

